WO2002096475A1 - Oxyde modifie - Google Patents

Oxyde modifie Download PDF

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Publication number
WO2002096475A1
WO2002096475A1 PCT/SE2002/001024 SE0201024W WO02096475A1 WO 2002096475 A1 WO2002096475 A1 WO 2002096475A1 SE 0201024 W SE0201024 W SE 0201024W WO 02096475 A1 WO02096475 A1 WO 02096475A1
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Prior art keywords
titanium
implant
calcium
oxide
anodic
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PCT/SE2002/001024
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English (en)
Inventor
Young-Taeg Sul
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Mediteam Dental Ab
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Application filed by Mediteam Dental Ab filed Critical Mediteam Dental Ab
Priority to KR1020037015650A priority Critical patent/KR100958958B1/ko
Priority to AT02736364T priority patent/ATE510567T1/de
Priority to DK02736364.7T priority patent/DK1397168T3/da
Priority to JP2002592983A priority patent/JP2005508862A/ja
Priority to EP02736364A priority patent/EP1397168B1/fr
Publication of WO2002096475A1 publication Critical patent/WO2002096475A1/fr
Priority to US10/724,096 priority patent/US7291178B2/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/3094—Designing or manufacturing processes
    • A61F2/30942—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/3094—Designing or manufacturing processes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00011—Metals or alloys
    • A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00598—Coating or prosthesis-covering structure made of compounds based on metal oxides or hydroxides
    • A61F2310/00616—Coating made of titanium oxide or hydroxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the present invention relates to calcium-containing, phosphor-containing and/or sulphur- containing osteoconductive/ osteoinductive titanium/titanium alloy implants based on surface oxide chemistry modifications of bone-anchored titanium/titanium alloy implants.
  • the invention also relates to a process of producing said implants.
  • Titanium metal is so far the most successfully osseointegrated implant material in long-term clinical performance [Adell R. et al., 1990].
  • Despite excellent biocompatibility of thin native oxide films on titanium implants [Kasemo B. et al., 1986 and Johansson C. B. 1991], however, it is generally known that native titanium oxide seldom forms a direct chemical bond to bone tissue (often defined as inert ceramic biomaterial) [Li J. et al., 1998].
  • Various surface processing technologies such as plasma spraying, simple immersion/soaking method, ion implantation beam associated deposition have been applied to improve biocompatibility of titanium implants.
  • anodic oxidation is a valuable process to enforce the multifactorial biocompatibility such as the oxide thickness, chemical composition, surface morphology, crystallinity, surface roughness change and dielectric constant of the surface oxide in titanium implants [Sul et al. 2000a and 2001b].
  • Michiaki et al. (1989) and Seishiro (1989) reported the thicker oxide layer in few micrometer to few tens of micrometer with few ⁇ m of pore size fabricated in the H 2 SO + H 3 PO 4 mixed electrolyte system.
  • WO 98/51231 discloses modified titanium oxide layers of about 10-200 ⁇ m and an increased surface oxide crystallinity and roughness.
  • U.S. 5,354,390 discloses a process of forming an oxide layer using anodic oxidation followed by a heat treatment.
  • WO 00/72775 discloses coatings including calcium phosphate compounds.
  • the surface of oxide layer on the titanium includes about 20 % titanium, about 55 % oxygen and 20 % carbon, the rest of the layer is composed of titanium oxide.
  • the used electrolytes are inorganic and organic acid, for instance the H 2 SO 4 + H PO 4 mixed electrolyte system.
  • Cross-sections of the titanium oxide layer disclosed in these documents show a very thick layer exhibiting a network of channels, extension of the channels and connected channel branches.
  • the purpose of the channels is mainly to allow the administration of a bone-stimulating agent.
  • the object of the present invention is to produce osteoconductive/osteoinductive oxide properties of titanium/titanium alloy implants, leading to faster and stronger osseointegration in clinical performance of bone-anchored titanium/titanium alloy implants and improved clinical success for long-term functional loading in the human body.
  • a osteoconductive/osteoinductive titanium/titanium alloy implant obtained by anodic oxidation, said implant comprises an additional element in the titanium oxide, wherein the additional element is chosen from the group consisting of calcium, phosphor or sulphur, said implant exhibits a cross-section of the calcium- incorporated osteoconductive/ osteoinductive oxide layer which consists of a double layer structure of an upper porous layer and a lower compact barrier.
  • the porous upper layer exhibits an open structure comprising a plurality of shallow craters.
  • One aspect of the invention provides a process of producing a osteoconductive/osteoinductive titanium/titanium alloy implant comprising an additional compound as a titanium oxide component, wherein the additional compound is chosen from the group consisting of calcium, phosphor or sulphur, using a electrochemical oxidation method, comprising the steps of: a) providing anodic electrochemical oxidation of the titanium/titanium alloy implant in an electrolyte containing at least one of said additional components, b) controlling the anodic forming voltage transient with slope (dV/dt), as to produce an oxide layer on said titanium/titanium alloy implant exhibiting a double layer structure of an upper porous layer and a lower compact barrier layer.
  • Another aspect of the invention provides a method of producing the implants according to the invention, wherein the additional element is chosen from the group consisting of calcium, phosphor or sulphur, comprising the steps of: a) controlling the anodic forming voltage transient with slope (dV/dt) of 2 to 0.3 dV/dt, oxide growth constant ( , nm/V), the current efficiency (nm.cm /C), the anodic oxide forming rate (nm/sec); b) controlling the intensity and extent of breakdown phenomenon and breakdown voltage, c) controlling the incorporation of either calcium, phosphorous or sulphur into the double layer structure of a upper porous and a lower barrier oxide layer by colloidal deposition mechanism, d) controlling reinforcement of the mechanical properties of said oxide containing an additional element for long term functional loading in the human body - to strictly confine the anodising time from the first onset of micro arcing phenomenon on the titanium/titanium alloy anode to near anodic forming voltage transient with slope d
  • Another aspect of the present invention provides a process of producing a osteoconductive/ osteoinductive titanium/titanium alloy implant comprising calcium as a titanium oxide component, wherein said titanium/titanium alloy implant is electrochemically anodically oxidised in (a) at least one calcium-containing electrolyte and (b) EDTA (ethylene diamine tetra acetic acid) to yield a calcium-containing implant.
  • EDTA ethylene diamine tetra acetic acid
  • Yet another aspect of the present invention provides a process of producing osteoconductive/ osteoinductive titanium/titanium alloy implants comprising phosphor as a titanium oxide component, wherein said titanium/titanium alloy implant is electrochemically anodically oxidised in at least one phosphor-containing electrolyte to yield a phosphor-containing implant.
  • a further aspect of the present invention provides a process of producing osteoconductive/ osteoinductive titanium/titanium alloy implants comprising sulphur as a titanium oxide component, wherein said titanium/titanium alloy implant is electrochemically anodically oxidised in at least one sulphur-containing electrolyte to yield a sulphur-containing implant.
  • the oxides produced by the process according to the invention demonstrate excellent mechanical strength and do not show a delamination of the oxide film and oxide particles internalised by the inflammatory cells such as microphage and multinuclear giant cell.
  • the implants in the present invention takes advantage of the stronger and faster osseointegration as proved in animal studies by strong bonding reactions between bone and the modified surface chemistry of titanium oxide by using process according to the invention, and consequently promote highly successful modality in clinical performance of osseointergrated titanium implants.
  • the implant surfaces in the present invention have the reinforced mechanical strength and overcome a drawback such as the biological delamiantion/ resorption of the coated calcium phosphate and hydroxyapatite on implants, resulting in clinical loosening of implants in bone.
  • Fig. 1. shows a schematic drawing of the equipment setup.
  • Fig. 2. shows the anode voltage increase in time.
  • the line shows three distinct zones with different slope: Zone 1 is linear with the highest slope; zone 2 is non-linear with slope dWdt > 0.3; and zone 3 is non-linear with dV/dt ⁇ 0.3.
  • Fig. 4. shows Transmission Electron Micrographs (TEM) of ultramicrotomed cross-sections of the three oxide layer types, in order to demonstrate the double layer structure of each consisting of the upper porous and lower barrier layer, respectively.
  • U upper porous layer with pores/craters
  • L lower barrier layer with no pores/craters
  • I titanium/oxide interface
  • Ti titanium bulk of the implant
  • D width of the pore
  • H height of the pore. Thickness of L»U and size D»H.
  • Fig.5. shows SEM pictures of the surface of Ca, P, and S implants, respectively.
  • Fig. 6 shows Light microscopic comparison between an implant produced by conventional anodic oxidation (fig. 6a) and a calcium-containing implant according to the present invention (fig. 6b).
  • fig. 6a internalised oxide particles (arrows) are clearly visible in macrophages but no oxide particles are present in 6b.
  • Fig. 7. shows High resolution X-ray Photoelectron Spectroscopy (XPS) at the Ca 2py , P 2p 3/2 , and S 2p peak positions of the Ca, P, and S implants, respectively.
  • XPS X-ray Photoelectron Spectroscopy
  • Fig. 8. shows Auger Electron Spectroscopic (AES) measurements of Ca, P, and S concentration depth profiles of the Ca, P and S implants, respectively.
  • U upper porous layer with pores/craters
  • L lower barrier layer with no pores/craters.
  • Fig. 9. shows X-ray Diffraction (XRD) angle measurements of the implants by this invention and control implants, respectively.
  • Fig. 11. shows mean values (%) of bone to metal contact (BMC) measurements of the implants according to this invention compared to control implants. ** indicates highly statistically significant differences (p ⁇ 0.001). Standard errors of the mean (SEM) are given as bars.
  • Fig. 12. shows light microscopic observations showing the much higher osteoconductive/ osteoinductive properties of the present implants (1, 4, and 6) when compared to control implants (2, 3, and 5).
  • the micro arc anodic oxidation (MAO) process produces osteoinductive/osteoconductive titanium/titanium alloy implants with additional components (additives: simple calcium, phosphorus, or sulphur compounds) electrochemically incorporated into the titanium oxide surface layer.
  • the MAO process according to the present invention was performed using an equipment provided with a titanium anode 1 and a platine cathode 2 in an electrolyte 3.
  • a DC power supply 4 was connected to a computer in which electrical current and voltage was recorded every 0.5 second.
  • the temperature was measured using a thermometer 6 and the desired temperature was maintained using a cooling system 5.
  • the electrolyte was stirred using a magnetic stirrer bar 7 on a magnetic stirrer plate 8.
  • the anodic oxide-forming voltage increases with time during three distinguishable phases ("zones") with different slopes dVl ⁇ t (Fig.
  • zone 1 the voltage increases linearly; zones 2 and 3 display transient slopes of dV/dt > 0.3 and dV/dt ⁇ 0.3, respectively. It was found (see below) that the best results were obtained by strictly confining the anodising time from the first onset of the MAO phenomenon to near the boundary between zones 2 and 3 in Fig. 2, where the slope of the anodic voltage transient is approximately 0.3. This was orchestrated by controlling the following parameters (Fig. 3), given in order of impact on the process: electrical current density > electrolyte concentration > surface area ratio of anode to cathode > electrolyte temperature > agitation speed > chemical composition of the titanium/titanium alloy electrode (ASTM grade 1- 4).
  • the oxide layer obtained contains lower concentrations of additives (L in the AES depth profiles of Fig. 8) than the layers obtained in zones 2 and 3, and the morphological structure is that of a dense nonporous barrier devoid of pores, craters, and channel networks. This is clearly seen in SEM and TEM micrographs (a in Fig. 2 and L in Fig. 4, respectively).
  • the thickness of this layer is usually between 200-1000 nm (Figs. 4 and 8).
  • This outer layer has a multitude of pores and craters (b and c in Fig. 2, Fig. 5, and U in Fig. 4) and a higher concentration of additives (U in Fig. 8). Furthermore, it is thinner in than the innermost layer with a thickness lower than 100 nm (Figs. 4 and 8), and on all MAO-treated surfaces studied the outer layer constituted less than 40% of the two layers taken together.
  • the chelating agent EDTA ethylene diamine tetraacetic acid
  • the pH adjusted to between 7 and 12 (examples 7-10 in Table 1).
  • Use of EDTA in this system requires an alkaline pH to give good mechanical properties of the oxide layer.
  • the Ca implants produced by the process according to the present invention were characterised with various surface analysis techniques.
  • the chemical composition of the Ca implant as measured by XPS clearly reveals that calcium is a main added constituent of the surface (Ca 2p in Fig. 7).
  • the spectrum shows a doublet peak from the Ca orbitals 2p ⁇ / 2 and 2p 3/2 at 351.4 eV and 347.8 eV, respectively (Ca implants)
  • the present Ca peak positions may indicate that Ca is present in calcium titanates such as CaTiO 3 .
  • AES measurements clearly demonstrate the concentration depth distribution of Ca throughout the oxide layer, which proves that calcium/calcium compounds incorporate into the titanium oxide during said process (maybe by a mechanism of colloidal deposition).
  • the relative atomic concentration of Ca is in the range of 0.5 to 48 %.
  • the outer porous layer exhibits between 11 % and 30 % porosity, preferably about 15 %.
  • porosity is defined a total area of the opening pores /a total of the scanned area x 100 in %.
  • the porosity was defined as the total area of the opening pores /the total scanned area (3 x 20 ⁇ m x 26 ⁇ m) in %.
  • the MAO process according to the present invention can also be used for producing phosphorus-containing implants (XPS surface analyses in Fig. 7).
  • the outer porous layer of the dual-layered oxide surface (U in Fig 4, and Fig. 5) has a thickness below about 1000 nm, preferably 100-500 nm.
  • the lower barrier layer (L in Fig 4) has a thickness between about 300 nm and 2000 nm, preferably 600-1500 nm.
  • the total thickness of both layers typically ranges from 300 to 3000 nm but should preferably be between 600 and 1500 nm (Ti and O in AES depth profile of Fig 8).
  • the outer porous layer exhibits between 11 % and 30 % porosity, preferably about 15 %.
  • the relative phosphorus concentration of the oxide layer of said implant is between 1 % and 30 %, preferably between 3 % and 15 % (P in AES depth profile of Fig. 8).
  • the relative phosphorus concentration amounts incorporated into the anodic oxide layer increases with layer thickness.
  • the crystal structure is amorphous, and/or amorphous and anatase, and/or amorphous, anatase, and rutile (XRD analysis in Fig. 9).
  • Phosphorus-containing electrolytes used in the anodising process are chosen from the group consisting of: phosphoric acid, glycerophosphate, sodium phosphate, sodium pyrophosphate, sodium phosphinate, ammonium phosphate, and potassium phosphate.
  • the porous outer layer (U in Fig. 4, and Fig. 5) has a thickness below 1000 nm and should preferably be 100-500 nm, with a porosity between 11-30 %, preferably about 15 %.
  • the lower barrier layer (L in Fig. 4) has a thickness between 300-2000 nm, preferably 600-1500 nm. Total thickness of both layers typically ranges from 300 to 3000 nm, preferably from 600 and 1500 nm (S in Fig. 8).
  • Relative sulphur concentration of the oxide layer is between 1 % and 30 %, preferably between 3 % and 15 % (Fig. 8).
  • the relative sulphur concentration/amounts incorporated into the anodic oxide layer increases with layer thickness.
  • the crystal structure is amorphous, and/or amorphous and anatase, and/or amorphous, anatase, and rutile (Fig. 9).
  • Sulphur-containing electrolytes used in the anodising process are chosen from the group consisting of: sulphuric acid, potassium sulphate, sodium sulphate, sodium thiosulphate, sodium hydrosulphite, and sodium pyrosulphite.
  • Said MAO process from the first onset of micro arcing phenomenon on the titanium/titanium alloy anode to near anodic forming voltage transient with slope dV/dt ⁇ 0.3, absolutely depends on specified combinations of major electrochemical parameters, especially the intrinsic nature and concentration of said electrolytes, the applied current density, and the electrolyte temperature.
  • any given example of specified combinations of major electrochemical parameters, especially the intrinsic nature and concentration of said electrolytes and the applied current density, are not limitative. In any cases, however, the whole anodising time did not take more than about 120 seconds.
  • the applied DC voltage was in the range from 30 V to 500 V.
  • the current density was in the range from 60 mA/cm 2 to 4000 mA/cm 2 .
  • the temperature was in the range from 9 °C to 100 °C.
  • the agitation speed of the electrolytes was in the range from zero rpm to 800 rpm.
  • the surface area ratio of the screw type of titanium anode versus the platinum counter electrodes was 3.5 %.
  • Examples 1-5 is the MAO process in single-component calcium electrolyte systems, the electrochemical parameters of which are summarized in Table 1.
  • Said MAO process started and ended as follows: for calcium acetate, calcium lactate, and calcium sulphate the first onset of the MAO started at 10-13 s. (in the range of approximately 210-230 V), 25-30 s. (approx. 180-200 V), 8-13 s. (approx. 120-150 V), and 10-13 s. (approx. 210-230 V), respectively.
  • For electrical current densities of 60-2000 mA cm 2 calcium / calcium compounds were incorporated into the anodic oxide film (maybe by a colloidal deposition mechanism). More particularly, the calcium amount of said calcium implants increased with the current density.
  • Examples 6-10 describe the MAO process performed in mixed calcium electrolyte systems, also summarized in Table 1.
  • Fig. 3 shows the combinations of major parameters used to control the process: the chemical nature and concentration of calcium-containing electrolytes, applied current density, electrolyte temperature, and agitation speed. Setting the current density to 60 mA/cm initiates the first onset of micro arcing phenomenon, which started at about 100 V (8 in Fig. 3) and ended up at 150 V (4 in Fig. 3). Correspondingly, for 300 mA/cm 2 it started at 130 V (7 in Fig. 3) and ended at 300 V (3 in Fig. 3); for 1000 mA/cm 2 it started at 260 V (6 in Fig. 3) and ended at 450 V (2 in Fig.
  • the MAO process according to the present invention is designed to regulate the intensity/extension of breakdown phenomena, using the anodic voltage transient with slope dV7dt as an important parameter.
  • the implant preparation process is characterized by an anodic voltage surge (Table 2), visible electric sparking on the anode surface, and gas evolution. Table 2. Examples of anodic voltage surge (within boxes).
  • Example 12 surface Ca, P, and S oxide chemistry
  • Example 13 Transmission Electron Microscopy (TEM) cross-sectional view.
  • the oxide films were crosscut using an ultramicrotome and the morphological structure, as seen in the TEM cross-sectional view of Fig. 4, demonstrated a double structure.
  • the upper porous layer (U in Fig. 4) was characterised by a lot of craters and is much thinner than the lower layer (L in Fig. 4).
  • the lower barrier layer did not include any pores/craters, extension of pore channels, network of channels or connected channel branches.
  • Example 14 oxide thickness
  • the oxide thickness was measured with TEM and AES.
  • the thickness of the calcium containing oxide layer consisted of the upper porous layer (U in Fig. 4) + the lower barrier layer (L in Fig. 4).
  • Total thickness of one calcium containing oxide layer, measured by the TEM cross-sectional view of Fig. 4, was approximately 300 nm; about 100 nm of U and 200 nm of L.
  • the oxide thickness of Ca, P, and S implants is 1296 ⁇ 225 nm, 1224 ⁇ 144 nm, and 1080 ⁇ 324 nm, respectively, measured with AES at one thread-top, one thread- valley, and in the bottom of the screw implant.
  • a thin-film X-ray diffractometer (TF-XRD, Rigaku Co.), equipped with a PW3020 goniometer was employed for analyses of the titanium oxide crystal structure. Angles were scanned between 20° and 80° with a step size of 0.04°. Spectra were recorded using Cu K ⁇ radiation (wavelength 1.54 A). Crystal structures of said calcium implants showed amorphous, anatase, and a mixture of anatase and rutile structures (Fig. 9).
  • Example 16 surface roughness
  • the surface roughness was measured with confocal laser scanning profilometer (TopScan3D ® ) as described by Wennerberg et al.
  • the surface roughness parameter S a (the height deviation from the mean plane) was 0.83 ⁇ 0.32 ⁇ m for control implants, 1.04 ⁇ 0.42 ⁇ m for S implants, 0.82 ⁇ 0.29 ⁇ m for P implants, and 0.85 ⁇ 0.32 ⁇ m for Ca implants.
  • the corresponding S cx values (the average distance between surface irregularities in the spatial direction) were 9.78 ⁇ 1.40 ⁇ m, 12.05 ⁇ 3.74 ⁇ m, 11.19 ⁇ 2.33 ⁇ m, 9.83 ⁇ 1.07 ⁇ m, respectively.
  • Example 18 - histomorphometry The histomorphometrical investigations involved (i) quantifications of the bone to metal contact (BMC) and (ii) the evaluation of tissue remodelling activity (a rough estimate of the osteoconductivity) [Johansson et al. 1998 and Sul et al 2001b]. Routinely stained undecalcified Toluidine blue sections (10-30 ⁇ m thick) were histomorphometrically analysed with a Leitz Aristoplan light microscope, which was equipped with a Leitz Microvid unit, connected to a PC, enabling the observer to perform quantifications directly in the eye-piece of the microscope, using a magnification of 10X and a zoom of 2.5X. The Ca implant demonstrated the strongest bone response regarding quantitative histomorphometry.
  • the mechanical strength of the oxide layer of anodised implants is an essential requirement for the usefulness and safety of clinical applications.
  • Calcium-containing oxides made by said MAO process demonstrated excellent mechanical strength.
  • the tensile strength of said oxide layer was shown to be 62 MPa (Table 3), which almost corresponds to a 100 % increase compared to 33MPa of SE 9901974-7 and to the range of 30 to 35 MPa of US 5478237 A.
  • Oxidised implants having thicker oxide layers than the present calcium implants showed a delamination of the oxide film and oxide wear particles scattered near the implant surface (maybe due to tear-off of the thicker oxide films) internalised by the inflammatory cells such as macrophages and multinuclear giant cells (Fig. 6a).
  • the thicker oxide layer obtained in or above zone 3 showed inferior mechanical properties such as microcracks (e in Fig. 2).
  • the porosity was defined as the total area of the opening pores /the total scanned area (3 x 20 ⁇ m x 26 ⁇ m) in %. In the table below the pore characteristics of screw implants is shown. The data was obtained using an image analysis of Scanning Electron Microscopy (SEM) negatives on 3 randomly selected areas with a scanning area of 20 ⁇ m x 26 ⁇ m.
  • SEM Scanning Electron Microscopy
  • PSD Pore number counted in the scanning area of 3 x 20 ⁇ m x 26 ⁇ m.

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Abstract

La présente invention concerne un implant réalisé en un alliage de titane/titane ostéoconducteur/ostéoconducteur comportant un élément supplémentaire dans l'oxyde de titane, obtenu par oxydation anodique. Ledit implant comporte un élément supplémentaire dans l'oxyde de titane tel que du calcium, du phosphore ou du soufre. L'invention concerne également un procédé de production desdits implants.
PCT/SE2002/001024 2001-05-29 2002-05-29 Oxyde modifie WO2002096475A1 (fr)

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KR1020037015650A KR100958958B1 (ko) 2001-05-29 2002-05-29 개질 산화물
AT02736364T ATE510567T1 (de) 2001-05-29 2002-05-29 Titanoxid haltiges implantat
DK02736364.7T DK1397168T3 (da) 2001-05-29 2002-05-29 Modificeret titanoxidflade af implantater
JP2002592983A JP2005508862A (ja) 2001-05-29 2002-05-29 修飾酸化物
EP02736364A EP1397168B1 (fr) 2001-05-29 2002-05-29 Implant de titane ayant en surface un oxide de titane modifie
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SE0104213A SE519600C2 (sv) 2001-05-29 2001-12-12 Titanimplantat innefattande ett tillsatselement i titanoxiden samt process för tillverkning av implantaten
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WO2004000378A1 (fr) * 2002-06-21 2003-12-31 Politecnico Di Milano Interface d'osteointegration pour protheses implantables et procede de fabrication
WO2004024202A1 (fr) * 2002-09-16 2004-03-25 Lynntech Coatings, Ltd. Implants biocompatibles traites anodiquement
WO2005087982A1 (fr) * 2004-03-13 2005-09-22 Accentus Plc Implants metalliques
WO2006004297A1 (fr) * 2004-04-26 2006-01-12 Korea Institute Of Machinery And Materials Implant metallique osseoinducteur pour corps vivant et procede de production
WO2007029602A1 (fr) * 2005-09-08 2007-03-15 Kinki University Matière de remplacement d'os, matière médicale contenant la matière de remplacement d'os et procédé servant à produire la matière de remplacement d'os
DE102008026557A1 (de) 2008-06-03 2009-12-17 Königsee Implantate und Instrumente zur Osteosynthese GmbH Elektrochemisch hergestellte, biologisch degradationsstabile, duktile und haftfeste Titanoxid-Oberflächenschicht auf Titan oder Titanbasislegierungen
DE102008026558A1 (de) 2008-06-03 2010-01-14 Königsee Implantate und Instrumente zur Osteosynthese GmbH Elektrochemisches Tauchverfahren in einem wässrigen Elektrolyt zur Erzeugung einer biologisch degradationsstabilen Oberflächenschicht auf Grundkörpern aus Titan oder Titanbasislegierungen
US7695522B2 (en) 2002-04-16 2010-04-13 Accentus Plc Metal implants
US20110303547A1 (en) * 2004-07-23 2011-12-15 Ilya Ostrovsky Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys
EP2532621A1 (fr) * 2010-01-27 2012-12-12 National University Corporation Tokyo Medical and Dental University Oxyde métallique, matériau métallique, matériau biocompatible, et procédé de fabrication d'oxyde métallique
EP1696816B2 (fr) † 2003-12-11 2013-10-30 Nobel Biocare Services AG Implant et/ou unite appartenant audit implant, et procede de production de l'implant et/ou de l'unite
US8597676B2 (en) 2007-07-09 2013-12-03 Astra Tech Ab Bone tissue implant comprising lithium ions
US8858775B2 (en) 2007-10-03 2014-10-14 Accentus Medical Limited Method of manufacturing metal with biocidal properties
US9744263B2 (en) 2007-07-09 2017-08-29 Astra Tech Ab Bone tissue implant comprising strontium ions
US11357600B2 (en) 2014-12-16 2022-06-14 Nobel Biocare Services Ag Dental implant
US12121414B2 (en) 2018-11-12 2024-10-22 Nobel Biocare Services Ag Dental implant, component for dental applications, implant system for dental applications, method for forming a protective layer on the surface of an implantable or implant component, implantable or implant component having a protective layer, and use of a protective layer

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JP5978650B2 (ja) * 2012-02-24 2016-08-24 Ｊｆｅスチール株式会社 鉄鋼材料の表面処理方法
CN109208050B (zh) * 2018-11-02 2021-03-30 山东金盛源电子材料有限公司 一种提高电解铜箔耐腐蚀性的表面处理方法

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US7695522B2 (en) 2002-04-16 2010-04-13 Accentus Plc Metal implants
WO2004000378A1 (fr) * 2002-06-21 2003-12-31 Politecnico Di Milano Interface d'osteointegration pour protheses implantables et procede de fabrication
WO2004024202A1 (fr) * 2002-09-16 2004-03-25 Lynntech Coatings, Ltd. Implants biocompatibles traites anodiquement
EP1696816B2 (fr) † 2003-12-11 2013-10-30 Nobel Biocare Services AG Implant et/ou unite appartenant audit implant, et procede de production de l'implant et/ou de l'unite
US9931184B2 (en) 2003-12-11 2018-04-03 Nobel Biocare Services Ag Arrangement with an implant and/or a unit belonging to said implant, and method for production of the implant and/or unit
US9011665B2 (en) 2004-03-13 2015-04-21 Accentus Medical Limited Metal implants
WO2005087982A1 (fr) * 2004-03-13 2005-09-22 Accentus Plc Implants metalliques
EP1740128A1 (fr) * 2004-04-26 2007-01-10 Korea Institute Of Machinery & Materials Implant metallique osseoinducteur pour corps vivant et procede de production
EP1740128A4 (fr) * 2004-04-26 2011-08-24 Korea Mach & Materials Inst Implant metallique osseoinducteur pour corps vivant et procede de production
WO2006004297A1 (fr) * 2004-04-26 2006-01-12 Korea Institute Of Machinery And Materials Implant metallique osseoinducteur pour corps vivant et procede de production
US8920869B2 (en) 2004-04-26 2014-12-30 Korea Institute Of Machinery And Materials Osseoinductive metal implants for a living body and producing method thereof
US20150209480A1 (en) * 2004-04-26 2015-07-30 Korea Institute Of Machinery And Materials Osseo-inductive metal implants for a living body and the producing method thereof
US9644284B2 (en) * 2004-07-23 2017-05-09 Chemetall Gmbh Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys
US20110303547A1 (en) * 2004-07-23 2011-12-15 Ilya Ostrovsky Method for producing a hard coating with high corrosion resistance on articles made of anodizable metals or alloys
WO2007029602A1 (fr) * 2005-09-08 2007-03-15 Kinki University Matière de remplacement d'os, matière médicale contenant la matière de remplacement d'os et procédé servant à produire la matière de remplacement d'os
US9744263B2 (en) 2007-07-09 2017-08-29 Astra Tech Ab Bone tissue implant comprising strontium ions
US8597676B2 (en) 2007-07-09 2013-12-03 Astra Tech Ab Bone tissue implant comprising lithium ions
US9889227B2 (en) 2007-07-09 2018-02-13 Astra Tech Ab Bone tissue implant comprising strontium ions
US8858775B2 (en) 2007-10-03 2014-10-14 Accentus Medical Limited Method of manufacturing metal with biocidal properties
DE102008026558A1 (de) 2008-06-03 2010-01-14 Königsee Implantate und Instrumente zur Osteosynthese GmbH Elektrochemisches Tauchverfahren in einem wässrigen Elektrolyt zur Erzeugung einer biologisch degradationsstabilen Oberflächenschicht auf Grundkörpern aus Titan oder Titanbasislegierungen
DE102008026557A1 (de) 2008-06-03 2009-12-17 Königsee Implantate und Instrumente zur Osteosynthese GmbH Elektrochemisch hergestellte, biologisch degradationsstabile, duktile und haftfeste Titanoxid-Oberflächenschicht auf Titan oder Titanbasislegierungen
EP2532621A4 (fr) * 2010-01-27 2014-07-09 Nat Univ Corp Tokyo Med & Dent Oxyde métallique, matériau métallique, matériau biocompatible, et procédé de fabrication d'oxyde métallique
EP2532621A1 (fr) * 2010-01-27 2012-12-12 National University Corporation Tokyo Medical and Dental University Oxyde métallique, matériau métallique, matériau biocompatible, et procédé de fabrication d'oxyde métallique
US11357600B2 (en) 2014-12-16 2022-06-14 Nobel Biocare Services Ag Dental implant
US11918434B2 (en) 2014-12-16 2024-03-05 Nobel Biocare Services Ag Dental implant
US12121414B2 (en) 2018-11-12 2024-10-22 Nobel Biocare Services Ag Dental implant, component for dental applications, implant system for dental applications, method for forming a protective layer on the surface of an implantable or implant component, implantable or implant component having a protective layer, and use of a protective layer

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ATE510567T1 (de) 2011-06-15
KR100958958B1 (ko) 2010-05-20
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